Environ. Sci. Techno/.
1995, 29, 439-445
Reductive Dechlorination of
Carlron Tetrachloride in Water
Catalyzed by Mineral-Supported
Biomimetic Cobalt Macrocycles
LJERKA UKRAINCZYK,*'+
M A L A M A CHIBWE,'
THOMAS J . PINNAVAIA,' A N D
STEPHEN A . B O Y D t
Department of Crop and Soil Sciences, and Department of
Chemistry and Center for Fundamental Materials Research,
Michigan State University, East Lansing, Michigan 48824
Reductive dehalogenation, mediated by nonspecific
biomimetic Co macrocycles, was studied in aqueous
systems using carbon tetrachloride as a model
compound. Two water-soluble macrocycles, cobalt
t e t r a k i s( N- m e t h y 1-4- p y r i d in iu my1) p or p h y r i n enzyme F430, and cobalamin (9-16). These macrocycles
(CoTMPyP) cation and cobalt tetrasulfophthalocyanine
(CoPcTs) anion, were used as homogeneous and
mineral-supported catalysts. The supported catalysts
were prepared by exchanging CoTMPyP on the
hectorite, fluorohectorite, and amorphous silica surface
and by exchanging CoPcTs on the layered double
hydroxide surface. Supported macrocycles were
catalytically active in the dechlorination of CC14 and
the initial reaction rates followed Michaelis-Menten
kinetics. The value of vmaxwas correlated t o the
previously reported orientation of macrocycles in the
interlayers and to the accessibility and electronic
state of the metal center, following the order: CoTMPyP-
silica > CoPcTs-layered double hydroxide > CoT-
MPyP-fluorohectorite > CoTMPyP-hectorite. In both
heterogeneous and homogeneous systems, volatile
reaction products accounted for less than 30% of CC14
degraded. In short-term experiments (2 h), homo-
geneous CoTMPyP was more active than heterogeneous
catalysts, while homogeneous CoPcTs was deacti-
vated due to aggregation, and degraded less CC14 than
supported CoPcTs. In long-term experiments (3
days), where large CC14/macrocycle ratios were used,
silica-supported CoTMPyP was more active than
homogeneous CoTMPyP, suggesting that adsorption ,
stabilized the catalyst.
0013-936W95/0929-0439$09.00/0 @ 1995 American Chemical Society
Introduction
Halogenated hydrocarbons are common soil, sediment, and
groundwater pollutants (1-5). Many halogenated hydro-
carbons are toxic, mutagenic materials that are resistant to
microbiological degradation and hence have long envi-
ronmental half-lives. The aliphatic carbon atoms bonded
to more than two halogens or the carbon atoms in aromatic
rings with high halogen substitution have high formal
oxidation states, which render such molecules resistant to
the degradation under aerobic conditions and susceptible
to a reductive degradation (1). This suggests the possibility
of using the reductive dehalogenation to detoxify haloge-
nated organic compounds. Certain anaerobic micro-
organisms reductively degrade such compounds by co-
metabolism; however, these processes are often slow and
require proper environmental conditions for microbial
activity and growth (6-8). Furthermore, high contaminant
concentrations may be toxic to the pollutant-degrading
bacteria (6, 7). In principle, the problem of toxicity can be
overcome by using biomimetic catalysts rather than live
cells. Reductive dehalogenation has been shown to be
mediated by transition metal macrocycles, such as co-
alongwith several other biomimetic complexes (12,13,17-
22) have been studied in homogeneous abiotic aqueous
systems as potential remediation catalysts for biomimetic
reductive dehalogenation of halogenated hydrocarbons.
Reductive dehalogenation catalyzed by biomimetic
macrocycles exhibits broad substrate specificity (10-13,
23). Among various metallated macrocycles, those con-
taining Co and Ni were found to be the most effective
catalysts (11-13). The catalytic activity of Co can be
attributed to its low spin electronic configuration in various
macrocycles and to the unique property of cobalt to form
metal-carbon bonds in water (24). The superior catalytic
activity of Ni appears to be limited to coenzyme F430, which
was shown to be more active than Co macrocycles (11,131,
while other Ni porphyrins exhibited lower catalytic activity
than Co porphyrins (12).
The implementation of homogeneous macrocyclic cata-
lysts in remediation technologies is impractical because of
problems with separating the aqueous catalyst, reactants,
and products. This problem could be overcome by
immobilizing macrocyclic complexes on a solid support.
There are numerous examples of supported macrocycles
and their applications in heterogeneous catalysis;however,
their application in aqueous systems has rarely been
investigated (22). Recently photoreductive dehalogenation
of aqueous bromoform has been shown to be catalyzed by
the anionic macrocycle (CoPcTs)adsorbed on the positively
charged titania surface (21).
High surface area minerals, such as layered clay minerals
and colloidal oxides, are attractive potential catalyst sup-
ports for environmental remediation in aqueous systems
from both an economical and practical point of view.
* Address correspondence to this author at his present address:
Department of Agronomy, Iowa State University, Arnes, IA 50011;
e-mail address: I-ukrain @ iastate.edu.
t Department of Crop and Soil Sciences.
*Department of Chemistry and Center for Fundamental Materials
Research.
VOL. 29. NO. 2. 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 439
 H3C- -CH3

CH3

COTMPyP CoPcTs
FIGURE 1. Structure of the cobalt tetrakis(l-metfiyl-4-pyridiniumyl)po~hyrin(CoTMPyP) cation and cobalt tetrasulfophthalocyanine(CoPcTs)
anion.

Investigation of these systems is of interest for remediation CoTMPyP-hectorite a

of industrial effluents and groundwater and for in situ
remediation of soils and sediments. The macrocycle must
carry a permanent charge to be adsorbed and retained on
II f
the charged surfaces of these supports. Synthetic cationic
p
co- -co- I 14.OA
and anionic porphyrins and phthalocyanines have been
intercalated into aluminosilicate clays and layered double
P
hydroxides (25-35). Unlike most neutral porphyrins (36-
381, cationic porphyrins are stable against demetallation CoTMPyP-fluorohectorite b
on the acidic clay surfaces (28).
Two macrocyclic catalysts, cationic CoTMPyP and
anionic CoPcTs (Figure l),were used in this study. These J
I 1
macrocycles have been previously intercalated in layered
minerals and characterized (35)byX-ray diffraction (XRD),
/////
o c o o c o OCO 0 c o 0 c o o
19.6A
electron spin resonance (ESR), and ultravioletlvisible ( U V / / / / / A 270
vis) spectroscopy. Their arrangements in the galleries of
layered supports are presented in Figure 2.
m
Carbon tetrachloride (CT) was chosen as a model
compound to study dehalogenation reactions by the C
supported macrocyclic catalysts because its biomimetic CoPcTs-layered double hydroxide
dechlorination in homogeneous systems has been studied I I
extensively. Although there are a number of studies on
reductive dechlorination of CT in water catalyzed by cobalt
macrocycles (10-1 4, la,the mechanismsof these reactions
are still not fuuy understood (16). Reaction schemes
1 l l l I I l
o c o o c o o c o o c o o coo c o o c o o 23.7A
involving Co(I1) (16) and Co(1) (14) as a catalytically active
species and the alkyl-cobalt intermediates have been
proposed. The volatile reaction products have been
identified, usually accounting from 20-30% (10,16)up to
50% (10,141of CT degraded. The major volatile degradation FIGURE 2 Arrangement of CoTMPyP in the interlayers of (a) hectorite
products are chloroform (CF) and dichloromethane (DM), and (b)fluorohectorite and of (c) CoPcTs in the interlayersof layered
double hydroxide (according to ref 35).
while usually only trace amounts of chloromethane,
methane, and carbon monoxide have been detected (10, The objectives of this study were to investigate whether
11, 14, 16). The homogeneous dechlorination reactions cationic and anionic Co macrocycles supported on high
have usually been performed in buffered solutions using surface area minerals maintain their ability to catalyze
dithiothreitol (DTT; 12,15, l a , titanium(II1) citrate (10,11, reductive dechlorination, to compare the rates of biomi-
13, 141, cysteine (191, sodium dithionate (201, or sodium metic reductive dehalogenation by homogeneous and
disulfide (19) as a reductant. Sodium dithionate was not heterogeneous macrocycles, and to investigate the long-
used in this study because it produces free radicals that term stability of supported catalysts.
destroy CoTMPyP (39). Sodium disulfide was used in the
preliminary experiments; however, difficulties were en- Materials and Methods
countered in buffering the pH. The experiments reported AU chemicals were reagent grade unless otherwise indicated
here were conducted using DTT as a reductant. and were used without further purification. CoTMPyP was

440 1 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2,1995

obtained as the tetrachloride salt from Midcentury Co,
(Posen, IL). CoPcTs was synthesized as the tetrasodium
salt by a published procedure (30,40). Natural hectorite
[M(Uo,dMg5,31Li0,1d(S$Ozo(OH,F)zl from Hector, CA, was
obtained in a spray-dried form from the Baroid Division of
NL Industries, The CEC of this clay was 0,7 mmok g-1(41),
Synthetic fluorohectorite [Li1.&4&1.&1.6) (Sh)O2oF41 was
prepared by crystallization of a fluorohectorite glass of
equivalent composition according to the general procedure
by B e d (42). The CEC of this material was 1,9 mmolc g-l
(43). Synthetic hydrotalcite-like LDH of the type [Mgdz-
(OH)14][CO3]x yHz0 was prepared bythe method ofReichle
etal. (44). Silica gel (chromatographic grade, Aldrich)with
a surface area of 500 m2 g-' was used without further
modifications.
Preparation of Supported Catalysts. Preparation of
layered catalystshas been described previously (35). Silica-
supported CoTMPyP was prepared by reacting 1 g of silica
gel suspended in 50 mL of water with 1 x mmol of
CoTMPyP for 24 h at pH 7.5 (adjusted with NaOH) under
nitrogen. The suspension was then centrifuged giving
colorless supernatant, indicating that all CoTMPyPhas been
adsorbed. The product was washed three times with water
and freeze-dried. The Soret band of suspended CoTMPyP-
SG was at 438 nm, and the complex was ESR silent,
indicating that Co was oxidized to Co(II1).
DechlorinationExperiments. Dechlorinationreactions
were studied using a modified method of Krone etal. ( 1I).
The reaction was carried out in a 2-mL anaerobic mixture
placed in a 10-mL glass vial crimp-sealed with a Teflon-
coated rubber septum (Hewlett-Packard)and wrapped with
aluminum foil. The vials were filled and sealed in an
anaerobic glovebox (Plas-Labs) under 10% H2/90% N2
atmosphere. In short-term experiments (reaction time is
2 h), the catalyst/reductant molar ratio was 1:lOOO (0.1mM
CoTMPyP or CoPcTslO.1 M DTT), and in the long-term
experiments (3 days) this ratio was 1:25000 (0.002 mM
CoTMPyP or CoPcTsl0.05 M DTT).
In short-term experiments, the homogeneous catalyst
was prepared as a 0.01 M stock solution and added by a
microsyringe. The heterogeneous catalyst was added by a
100-pL pipet as an aqueous suspension (0.55 wt % suspen-
sion of CoTMPyP-FH, 1.03wt % suspension of CoTMPyP-
H, 0.34 wt % suspension of CoPcTs-LDH). CoTMPyP-SG
was added as a solid (0.020@. Dithiothreitiol(Mallinckrodt)
was added as a solid. Freshly prepared, deoxygenerated,
and autoclaved 0.1 M sodium phosphate buffer (pH 7.5)
was added by a pipet, and the vials were sealed. Reaction
was initiated by injecting freshly prepared CT (99.9%,
Burdick & Jackson) stock solution (0.062MI in 2-propanol
through a septum 5 min after assembling the reductant/
catalystlbuffer mixture. The vials were shaken on a
controlled temperature rotary shaker at 25 "C for a desired
period of time.
In long-term experiments, the catalyst was added by a
microsyringe (homogeneous) or pipet (heterogeneous) to
75 mL of the phosphate buffer, and 2 mL of this mixture
was pipetted into 10-mL glass vials. The other reactants
were added as in short-term experiments. The experiments
were performed in duplicate, and each vial was analyzed
only once. One control, containing CT and DTT in
phosphate buffer, was run for each time point. Two random
controls were runas well: one containing CT and supported
catalyst in phosphate buffer, and the other containing CT
and the phosphate buffer. The loss of CT from the controls
was less than 1%in all short-term experiments (after 2 h)
and less than 4% in all long-term experiments (after3 days).
To test whether the dechlorination is catalyzed by the
complex at the interface, the reacting suspension in short-
term experiments was filtered after approximately 30 min
in the glovebox through a 0.1-pm Teflon filter into another
vial containing 0.015 g of solid DTT. The vials were sealed,
and the degradation of CT was followed for 2 h. Although
the filtrate was weakly colored (indicating some of the
macrocycle was desorbed from the support and/or some
of the colloidal particles passed through the filter),less then
2% of CT was dechlorinated in a 2-h time period, implying
that the macrocycle did not leach into liquid phase in a
significant amount.
The kinetics of CT degradation and the appearance of
CF and DM was followed by headspace analysis using a
Varian gas chromatograph with a DB-625 (0.25 mm i.d. x
30 m, J&W Scientific) column and a flame-ionization
detector. The column temperature was 35 "C, injector
temperature was 200 "C, and detector temperature was
250 "C. Headspace was sampled manually using a 0.1-mL
gas-tight syringe. The peak identification and quantifica-
tion were done using external standards made in 0.1 M
phosphate buffer. In the preliminary experiments, it was
determined that the peak areas of the standards were not
affected by the presence of the solid catalyst in the amount
used in this study.
Results and Discussion
Short-TermExperiments. Kinetic data for CT degradation
in six representative systems (homogeneous CoTMPyP,
CoTMPyP-FH, CoTMPyP-H,CoTMPyP-SG, homogeneous
CoPcTs, CoPcTs-LDH) are shown in Figure 3. All of the
supported macrocycles were catalytically active. CF and
DM were detected by the headspace analysis as the
degradation products in homogeneous systems,while only
CF was detected in the heterogeneos systems even at
reaction times greater than 2 h. The volatile products
accounted for less than 30% of CT degraded, which is
consistent with previous studies of CT degradation medi-
ated by c o macrocycles (10, 1 1 , 13, 16, 19).
The heterogeneous degradation of CT catalyzed by Co
macrocycles illustrated in Figure 3 can be described by the
first-order kinetics:
The pseudo-first-order rate constants (kobs)were calculated
(Table 1) by fitting the integrated form of the eq 1 to the
data in Figure 3. The observed pseudo-first-order rate
constant (kobs) may conceptually be separated into two
constants: kl, a pseudo-first-order rate constant for the
formation of CF, and k2, a pseudo-first-order rate constant
for the formation of unidentified products (includinglong-
lived intermediates): kobs = kl +
k2. Then the rate of
appearance of CF is
where k3 is a pseudo-first-order rate constant for CF
degradation. The rate of formation of DM is
VOL. 29, NO. 2. 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY I 4 4 1
 aggregation (30, 331, and thus the rate of heterogeneous
degradation does not show the rapid decrease in activity.
At the same total catalystlCT molar ratio (l:lO), the
0.6 1\ 1 degradation rates in CoTMPyP systemswere slower for the
0.4 heterogeneous systems than the homogeneous system,
0.2

0.0
0 30 60 90 120
O.* 0
0.0 u 30 60 90 120
following the order: CoTMF'yP CoTMPyP-SG CoT-
MPyP-FH > CoTMPyP-H. Adsorption on clay surfaces has
often been shown to alter the reactivity, mobility, and redox
properties of transition metal complexes and enzymes (41,
1.o 1 .o 43, 46, 4 7)
I

C.
0.8
Reactions catalyzed by macrocycles at the clay or silica
surface can differ from homogeneous reactions as a result
0.6
of changes in the redox potential of the supported mac-
0.4 rocycles as well as a result of the geometricalarrangements
0.2 0.2
ofthe macrocycles at the interface, which may yield different
product distribution. The lack of formation of DM in the
0"E 0.0
0 30 60 90 120
0.0
0 30 60 90 120 heterogeneous systems in this study is most likelythe result
of a change in the reduction potential of the supported
macrocycles to a more positive value relative to the aqueous
macrocycles. Since the dechlorination of CF to DM has
lower reduction potential [B&FIDM) = f0.439 V at pH
7, calculated from free energies of formation in liquid state,

0.2
0'4
0.0 w
0 30 60 90 120
I 0 30 60 90 (20
1 M C1- aqueous solution; 11,481 than the dechlorination
ofCT to CF [Bo(CTICF)= +0.516Vl, thereduction potential
of a supported Co macrocycle may be too high to drive the
reduction of CF to DM.
Furthermore, in solution both axial positions on Co are
Time (min) available for reaction while in the supported system the
FIGURE 3. Degradation of 1.0 mM CT (0)and production of CF (0) reactants may only have access to one of the Co axial
and DM (v) at pH 7.5 catalyzed by 0.1 mM Co macrocycle: (a) positions. The quantitative information on the changes in
homogeneous CoTMPyP, (b) CoTMPyP-FH, (c) CoTMPyP-H, (d) product distribution can be obtained from the ratio of the
ColMPyP-SG, (e) homogeneous CoPcTs, and fl) CoPcTs-U)H. Cutves rate constant (Table 1) for the formation of CF (kl) to the
represent simulation of the CT dechlorination and CF and DM
formation, based on the kinetic model presented in eqs 1-3. overall rate constant for CT degradation (kobs): the smaller
this ratio, the lower the tendency for the formal two-electron
TABLE 1 transfer from CT to Co and for CF formation. Alkyl radicals
('CC13 and 'CHCl3) or carbanions formed from CT and CF
Pseude=First=OrderRate Constants ( x 103)for by one electron reduction (10)instead of donating another
Degradation of CT and Product Formation Catalyzed electron to Co and reacting with the hydrogen ion to form
by Hoatogeneous and Heterogeneous Macrocycles CF and DM may be reacting with water to give CO and
hbs ki k2 4 k, formic acid as well as reactingwith each other and with the
catalyst (min-l)O SEb (inin-')' (min-')' (min-l)' ( m i d ) ' organic reductant to give nonvolatile products (10,11, 14,
CoTMPyP 52.2 4.8 26.5 25.7 7.9 5.8
16).
CoTMPyP-FH 8.0 0.2 1.5 6.5 1.1 ndc Plot of the initial rate (& = ko[CC&lo)of CT degradation
CoTMPyP-AS 31.4 2.3 9.9 21.5 1.2 nd by the supported macrocycles as a function of the initial
CoTMPyP-H 6.4 1.0 0.6 5.8 1.0 nd concentration of CT ([CC&l0)is shown in Figure 4. The
CoPcTs 45.8d 7.5 nfe nf nf nd initial rate constants (b) for heterogeneousCT degradation,
CoPcTs-LDH 28.9 1.3 12.8 16.1 4.3 nd
calculated by fitting the first-order rate equation to the data
a Rate constants kbs, k,,k2,and k, obtained by fitting eqs 1-3 to the for the first 30 min of the experiment, decrease in the order
data in Figure 3. Standard error for k b r . CH2C12was not detected.
Initial rate constant. Not fitted because the reaction could not be COTMQP-SG> COPCTS-LDH > COTMQP-FH> COTMQP-
described by the first-order kinetics. H.
It can be assumed that in the initial stages of the reaction,
the concentration of CT is much higher than the concen-
(3) tration of any of the reaction products, and thus the product
competition for the reactive sites can be neglected. At-
where k4 is a pseudo-first-order rate constant for the tempts to measure the amount of CT adsorbed in the
formation of DM. Equations 1-3 were solved by the suspensions containingonly the supported catalyst without
Runge-Kutta method using the k&s from the Table 1 and the reductant were unsuccessful because the amount
fitting k2, k3 and k4 values to the data (Table 1). The adsorbed was too small. Apparently the decrease in CT
calculated curves are shown in Figure 3 for all the systems concentration in the heterogeneous systems can be at-
studied, except homogeneous CoPcTs. In the homoge- tributed solely to its chemical degradation. The reductant
neous CoPcTs system,the fast initial rate rapidly decreases is then necessary in order to generate catalytically active
(Figure3e),indicatingthat the catalyst is beinginactivated. Co species.
The fast decrease in the catalytic activity of this macrocycle Spectroscopicstudies have shown that Co is present as
has been attributed to the aggregation of CoPcTs in aqueous Co(I1) in the intercalated macrocycles under both 0 2 and
solutions (45). Intercalation stabilizes CoPcTs against NZatmosphere (35). Since the supported catalyst exhibits

442 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2,1995

 61 I I
1 i
R (mMh')
0 0.5
FIGURE 4. Plot of the initial rate of degradation of CT in heterogeneous systems as a function of the initial
mM catalyst, 0.1 M DTr). Curves represent the Michaelis-Menten model (eq 4).
TABLE 2
Michaelis-Menten Parameters for CT Degradation
by Heterogeneous Catalysts
catalyst rU0 (mMl v, (mM h-?
CoTMPyP-FH 4.48 6.60
CoTMPyP-SG 5.87 17.28
CoTMPyP-H 2.34 1.OB
COPCTS-LDH 5.41 10.41
no activity in the absence of the reductant, the reduction
of Co(I1) to Co(1) by DTT may have to take place in order
to produce a catalytically active Co species. Adsorption of
CT onto the catalyst and the formation of the Co-CC13
intermediate in the heterogeneous systems depends on
the number of reduced Co sites and their accessibility to
the reactants. The decrease in k~ with increased CT
concentration (Figure 4) indicates that there is a limited
number of easily accessible active sites. The concentration
of the intermediate complex at the initial stages of the
reaction is small compared to the concentrations of Co
macrocycle and CT. Thus, the dechlorination reaction in
heterogeneous systems is very similar to enzyme-catalyzed
reactions, and the initial rate of CT degradation (Figure 4)
can be fitted by the Michaelis-Menten kinetic model:
(4)
where ,v is the maximum reaction rate for a specified
initial Co macrocycle (enzyme) concentration and Km is
Michaelis constant.
The value of 'K (Table 2) greater than 1implies that the
rate of formation of the intermediate complex is slower
than the rate of desorption of the products in all the
supported systems (49, 50). At longer reaction times, CT
concentration decreases, while CF and other reaction
products compete for the active surface sites, which
increases K,. When K, >->[CCL],eq 4 reduces to the first-
I I I 1
coTMP
COPcTs-LDH
1 1.5 2 2.5 3
[CCI~IO
(mM)
CT concentration (pH 7.5,O.l
order rate equation. The value of ,,v (Table 2) is
proportional to the surface density of catalytically active
sites, following the order CoTMPyP-SG > CoPcTs-LDH >
CoTMPyP-FH > CoTMPyP-H. For layered supports, this
order is in good agreementwith the results from the previous
spectroscopic studies on the orientation and hydration of
the macrocycles in the interlayers (Figure 2; 35).
The lowest reaction rates were observed for the CoTMPyP
supported on the low charge density clay hectorite, where
the macrocycle is lying parallel to the clay layers. The ESR
spectra of Co(I1)TMPyP intercalated in hectorite clearly
show that Co has no water in the axial coordination sites
and its d orbitals, interactingwith electron-deficient siloxane
oxygens, are contracted (33, indicating that it is likely to
be kinetically inert in electron-transferreactions (51). Water
does not diffuse into the CoTMPyP-H interlayers when the
clay is fullywetted, and apparently reactants cannot access
the interlayers either. Only a small portion of the Co(I1)-
TMPyP, adsorbed on the clay edges and outer surfaces, has
water in axial coordination sites, and those are most likely
the only catalytically active sites in CT dechlorination.
Intercalated CoTMPyP in a high-charge density clay fluo-
rohectorite is lying at a 27" angle to the clay layers with
water in the axial coordination sites. The electronic
configuration of aqueous CoTMPyP and CoTMPyP-FH are
very similar ( 3 3 ,and the ESR study shows that water diffuses
easily in and out of the clay interlayers. Therefore, the
decrease in activity for CoTMPyP-FH compared to the
aqueous CoTMPyP can be attributed to the slower rates of
adsorption of CT on active metal centers in the interlayers.
This may be due to the restricted mobility of reactants in
the clay interlayers as well as to the smaller number of
reduced metal centers because of the restricted access of
DTT to the macrocycles in the interlayers. Silica-supported
CoTMPyP exhibits the highest activity among supported
macrocycles. Metal centers of the macrocycles supported
on the spherical silica particles may be more active than
on the other supports because they are more accessible to
the reductant and to the reactants and possibly because
VOL. 29, NO. 2, 1995 I ENVIRONMENTAL SCIENCE & TECHNOLOGY 448
 TABLE 3
Pserdo=First=OrderRate Constants for CT
Degradation and Turnover Frequencies in Long=Term
Dechlorination Experiments
::b
0.0
-
j 0.8

catalyst
ICCl410
(mM)
k
(day-')* SEb
turnover
frequency (day-')c
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
CoTMPyP 2.3 0.49 0.06 570
CoTMPyP-FH 2.3 0.47 0.08 540
COTMPyP-SG 2.3 0.57 0.07 655
CoTMPyP-H 2.3 0.09 0.01 105

-e
16 CoPcTs 2.3 0.75 0.09 860
COPCTS-LDH 2.3 0.29 0.67 335
CoTMPyP 4.6 0.28 0.06 640
0.8 CoTMPyP-SG 4.6 0.39 0.04 895
8 0.4
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0
0.4 lLE!%zd
0.0 0.5 1.0 1.5 2.0 2.5 3.0
*
*Calculated forthefirst24 h ofexperioments. Standarderror. 0 Mol
of CCl,mol of catalyst-' day-'calculated for the first 24 h of experiment.

1.6
12

0.0 0.5 1.0 1.5 2.0 2.5 3.0

!im
12
0.8

0.4
0.0

Time (days)
i_,vr""i
0.0 0.5 .1.0 1.5 2.02.5 3.0
FIGURE 5. Degradation of 23 mM CT (0)and production of CF (0)
at pH 7.5 catalyzed by 0.002 mM 60 macrocycle: (a) homogeneous
CoTMPyP, (b) CoTMPyP-FH, (c) CoTMPyP-H, (d) CoTMPyP-SG, (e)
homogeneous CoPcTs, and (f) CoPcTs-LDH.
the reduction potential of Co is less altered on this surface
as compared to highly charged layered mineral surfaces.
Long-Term Experiments. The effect of immobilization
of the macrocycles on the solid support on the loss of their
catalytic activity with time was investigated in long-term
experiments (Figure5). The experiments were performed
with low catalyst amounts (0.002 mM) and high CT
concentrations (2.3 and 4.6 mM). The homogeneous
CoPcTs catalystwas not deactivatedunder those conditions,
because the aggregation of CoPcTs does not occur in very
dilute solutions. After 1 day, the reaction did not follow
the first-order kinetics because the catalysts had lost some
of their activity. Thus, the first-order rate constants and
turnover frequencies (mole of CT degraded per mole of
macrocycle per day) were calculated for the reaction time
of 1 day (Table 3).
Among the supported catalysts, CoTMPyP-SG exhibited
the highest activity, and CoTMPyP-H exhibited the lowest
activity. The frequency turnover was greater for CoTMPyP-
SG than for the homogeneous CoTMPyP (Table 31, indicat-
ing that adsorption on silica surface has significantly
increased catalyst longevity. For other supports (H, FH,
and LDH), turnover frequencies were less than those of the
corresponding homogeneous catalyst. With the exception
of hectorite, the loss of catalytic activity of the Co mac-
rocycles does not seem to be promoted by adsorption on
the solid. In fact, the homogenous CoTMPyP has lost its
activity after 2.5 days while the CoTMPyP-FH and CoT-
MFyP-SG systems were still active.
The smaller turnover frequency of CoTMPyP-FH than
that of homogeneous catalyst over the first 24 h of
experiment is consistent with the decreased rates observed
in short-term experiments for supported macrocycle. Thus,
the slower rates can be attributed to the slow rates of
adsorption of CT on reactive porphyrin metal centers in
the interlayers rather than to the loss of catalyst longevity
of the macrocycle upon intercalation. Low turnover
frequency exhibited by hectorite-supported CoTMPyP may
be attributed in the inaccessibility of the intercalated
porphyrin and to the alteration of the electronic state of
the metal center (35).
The hydration and electronic state of Co(1I)PcTs inter-
calated in LDH are similar to that of CoTMPyP-FH. This
macrocycle is perpendicular to the layers of LDH, providing
a more open structure and thus more easily accessible metal
center as compared to CoTMPyP-FH, which may partly
explain the higher dechlorination rates. In addition, the
difference in dechlorination rates between CoTMPyP-FH
and CoPcTs-LDH may partly arise from the difference in
the catalytic activity of two macrocycles in CT dechlori-
nation exhibited in the homogeneous systems (Figure 5a
and d; Table 3).
Corclusions
The study demonstrates that the supported macrocycles
are catalytically active under ambient conditions. The
heterogeneous dechlorination reactions can be described
by the first-order kinetics with the pseudo-first-order rate
constants being correlated to the accessibility and the
hydration of the cobalt in supported macrocycles, following
the order: CoTMPyP-SG > CoPcTs-LDH > CoTMPyP-FH
> CoTMPyP-H. The reaction mechanism may be similar
to enzyme-catalyzedreactions where the rate-determining
step is adsorption of CT on the active center with the
formation of the intermediate complex. Although initial
heterogeneous dechlorination rates were less than the
corresponding homogeneous rates, increased longevity of
supported catalysts led to greater dechlorination in reac-
tions catalyzed by CoTMPyP-SG and CoTMPyP-FH than
by homogeneous CoTMPyP at longer reaction times.
The charged, mineral-supported macrocycles reduc-
tively dechlorinate carbon tetrachloride in water, even at
high concentrations that would inhibit microbial activity.
Since the reduction potential of the macrocycles can be
altered by choosing the appropriate substituents on the
periphery of the porphyrin or phthalocyanine ligand,
efficient supported catalysts could be designed for reductive
dehalogenation by synthesizing macrocycles with tailored
redox properties.

444 rn ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2, 1995

Acknowledgments
This research was supported by the National Institute for
EnvironmentalHealth Sciences Grant P42EF0491, Michigan
State University Institute for Environmental Toxicology,
and Michigan Agricultural Experiment Station. We thank
Dr. Max M. Mortland for helpful discussions.
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Received for review May 10, 1994. Revised manuscript re-
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ES9402821
@ Abstract publishedin AdvanceACSAbstructs, December 15,1994.
VOL. 29, NO. 2, 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 1445